Phosphorus- and sulfur-containing complex metal salts of oxidized hydrocarbons and oil compositions thereof



United States Henry G. Berger, Glen Rock, Ferdinand P. Otto, Woodbury,and John W. Schick, Camden, N. J., assignors to gocillny Mobil OilCompany, Inc., a corporation of New No Drawing. Application December 23,1955 Serial No. 554,930

22 Claims. (Cl. 252-32.7)

The invention relates to a new class of phosphorus-, sulfurandmetal-containing oxidized hydrocarbon products and to a method for thepreparation of these products. It also contemplates the use of these newproducts as addition agents for mineral lubricating oils, particularlyoils designed for use in internal combustion engines.

It is well known that hydrocarbon lubricating oils tend to oxidize inuse in an engine with attendant formation of oxidation products whichare acidic in character and which exert a corrosive action on the engineparts, such as the hard metal alloy bearings. Furthermore, it is wellknown that the gradual deterioration of the oil in use due to oxidation,etc. is attended by formation of carbonaceous sludge and lacquer whichadheres to the engine parts, particularly the piston ring grooves andskirts, thereby lowering the efiiciency of the engine and frequentlycausing the rings to stick. To counteract these conditions, the art hasdeveloped chemical agents which when added in small amounts to enginelubricating oils have the ability to greatly retard the oxidation of theoil in use. Agents have also been developed which have the ability toprevent deposition of sludge materials on the engine parts, therebykeeping the engine clean and free from the clogging and sticking effectsnormally encountered. These two types of chemical agents are known inthe art as antioxidants and detergents, respectively. The presentinvention provides a new class of chemical products which exhibit bothantioxidant and detergent properties.

In a copending application, Serial No. 441,626, filed July 6, 1954,there is disclosed and claimed a method for oxidizing hydrocarbon oilsin the presence of metal hydroxides to produce complex metal salts ofthe oxidized oils which are effective detergents for mineral lubricatingoils.

It has now been found, in accordance with the present invention, that byreacting a hydrocarbon, such as a petroleum oil, which has been oxidizedin the presence of a metal hydroxide, with a phosphorus sulfide, andthen subjecting the resulting product to reaction with additional metalhydroxide in the presence of water, under the conditions hereinafterdefined, a new class of reaction products are produced. These newproducts have high metal contents. They also contain substantial amountsof phosphorus and sulfur and they exhibit exceptional detergentproperties, as well as being effective antioxidants for minerallubricating oils.

Due to the complex nature of the products provided by the invention, noexact chemical formula can be ascribed to them at this time and theyare, therefore, best described by the process of producing them. As faras atent P 2,830,949 Patented Apr. 15, 1958 is known, the products ofthe character provided by the invention have not been known heretofore.They are, therefore, believed to be new compositions of matter.

It is, therefore, the primary object of the invention to provide a newclass of phosphorus-, sulfurand metalcontaining oxidized hydrocarbonproducts. It is also an object to provide mineral lubricating oilscontaining minor amounts of these new products, said oils havingimproved antioxidant and detergent properties. Other and further objectswill be apparent from the following description.

It will be seen that broadly stated the present invention provides amethod for the preparation of oil-soluble, phosphorus-, sulfurandmetal-containing reaction products which involves the steps of (1)forming a mixture of a hydrocarbon material, such as a petroleum oil,and a metal hydroxide, (2) contacting said mixture with an oxidizing gasat a temperature of from about C. to about 325 C. to provide ametal-containing oxidized hydrocarbon product, (3) reacting themetal-containing oxidized hydrocarbon product with a phosphorus sulfideto provide a metal-, phosphorusand sulfur-containing oxidizedhydrocarbon product, (4) forming a mixture of the product produced instep 3 with water and a metal hydroxide at a temperature below theboiling point of water, (5) substantially completely dehydrating themixture formed in step 4 and (6) filtering the dehydrated mixture fromstep 5 to remove insolubles therefrom.

As aforesaid, the exact nature of the products produced by the processof the invention is not known, however, analytical data indicate thatthese products are comprised principally of complex salts, i. e., saltscontaining more equivalents of metal than so-called normal salts. Thus,it has been found that products produced by the oxidation step of theprocess contain about two equivalents of metal per equivalent ofacid-hydrogen formed in the course of the oxidation. For example, whensuch an oxidation product, prepared by oxidizing a petroleum oil andcontaining 1.50% calcium, was de-metallized by means of stronghydrochloric acid, the resulting acidic product had a neutralizationnumber (N. N.) of 21 and a saponification number of 18. Thisneutralization number would account for only 50% of the calcium,assuming the formation of normal salts. This indicated that theremaining 50% of the calcium is present in the product as some type ofcomplexed or coordination compound.

When the products produced in the oxidation step are reacted withphosphorus sulfide and the resulting products reacted with additionalmetal hydroxide in accordance with the subsequent steps of theinvention, the metal contents thereof are substantially increased. Themanner in which this further amount of metal is incorporated into theultimate products is not fully understood. However, without intending tolimit the invention in any way by theoretical considerations, it wouldappear that the phosphorus sulfide reacts with oxygenated groupscontained in the oxidized hydrocarbon molecules, such as aldehyde,ketone or alcohol groups, to form cross-linked molecules. As shown inthe examples presented hereinafter, the phosphorus sulfide reaction withthe oxidized hydrocarbon intermediate is often attended by substantialgel formation, particularly where the hydrocarbon reactant has beensubjected to relatively strong oxidation. This gel is broken by thewater which is always added to the reaction at this point in theprocess. It appears, therefore, that in the presence of water, thecross-linked molecules are hydrolyzed to form new acids which react withadditional 'me'tal hydroxide to produce the ultimate complex saltproducts of the invention. As in the case of the oxidized oilintermediate products, de-metallization of the final products indicatesthat their metal contents are greater on an equivalent basis than themetal contents of normal salts. Thus, such a product, containing 3.07%calcium, upon de-metallization with hydrochloric acid showed aneutralization number (N. N.) of 15. This acid number would account-foronly 054% calcium, assuming the formation of normal salts. This product,therefore, had a calcium content amounting to 500% excess orapproximately 5 equivalents of calcium over that which would be expectedin a normal salt product.

THE REACTANTS The hydrocarbons utilizable as starting materials in theprocess of the invention may comprise any hydrocarbon or mixture ofhydrocarbons capable of providing a product which is soluble inlubricating oil. In general, this solubility requirement is satisfied byhydrocarbons havingmo'lecular weights of from about 200 to about I000,with those having molecular weights of from about 600 to about 1000being particularly suitable. The hydrocarbons may be aliphatichydrocarbons of either the straight-chained, branch-chained or cyclictype. Also, aromatic hydrocarbons which have aliphatic substituentgroups of sufficiently high melocular Weight to provide anoil-solubilizing character to the final products can be used. Thus,alkaryl type hydrocarbons containing at least one aliphatic substituentof at least about 8 carbon atoms, or several such substituents totalingat least about 8 carbon atoms per molecule are suitable. Examples ofthese would be octyl benzene, dodecyl benzene, wax benzene, etc.

Petroleum oils and petroleum oil fractions, such as petrolaturns, waxes,etc., are a preferred class of hydrocarbon reactants, while refinedoils, such as Bright Stocks are especially preferred. In terms ofviscosity, oils having viscosities ranging from 2 to about 65centistokes at 210 F. may be used, with those having viscosities of fromabout to 45 centistokes at 210 F. being preferred. The characteristicsof several different types of suitable oil stocks are-shown in Table I.

Table I Gravity K. V. Av 011 API' 210 F., m

Solvent-refined Mid-Continent idlisttllate stock came MION U100 Themetal hydroxides utilizable as reagents in the invention are those ofthe metals of Groups I and II of Mendeleefis Periodic Table of theElements. Specifically, the hydroxides of calcium, sodium, barium,cobalt, strontium, zinc and magnesium are highly suitable, with calciumhydroxide being particularly preferred. Various grades of calcium oxide,calcium hydroxide and barium hydroxide may be used in the invention.However, grease-makers lime (96% CaOH) is preferred because of its highpurity, small particle size and its property of'being wetted by-oil.

The phosphorus sulfide reactant used in the process may be either P 8 PS 'or P 8 with phosphorus penta- '4 sulfide being preferred. Mixtures ofthe sulfides can also be used.

PROCESS CONDITIONS in conducting the oxidation step of the process, thehydrocarbon reactant and the metal hydroxide reagent are charged to areactor having means for the introduction of an oxidizing gas, such asair or oxygen. The amount of metal hydroxide charged to the hydrocarboncan range from about 0.5% up to about 25%, based on the weight of thehydrocarbon reactant. The reactants are mixed together and heated at atemperature of from about C. to about 325 C., preferably C. to 225 C.,and maintained at this temperature while the oxidizing gas is passedthrough the mixture to effect oxidation of the hydrocarbon and reactionof the oxidized hydrocarbon with the metal hydroxide. The oxidation iscontinued until the hydrocarbon has attained a metal content of fromabout 0.05% to about 3%, by weight. It has been found that superior oildetergents are provided by the process of the invention when arelatively mild oxidation is used, i. e., an oxidation which provides anoxidation product which has a metal content of from about 0.05 to about0.5 and preferably about 0.1%. Furthermore, the products obtained usinga mildly oxidized intermediate are better from the standpoint ofantioxidant ability.

It should be noted that the amount of metal hydroxide charged to thehydrocarbon prior to the oxidation reaction should, in all instances, bein excess of that eventually utilized in the oxidation. Thus, we havefound that at least about 15% of the metal hydroxide charged shouldremain unreacted at the end of the oxidation. It has been found that themetal hydroxide when present in such amounts serves to preventundesirable side reactions, such as oxidative polymerization, which aredetrimental to the provision of products of the nature and qualityherein-contemplated, particularly from the standpoint of color andsolubility in lubricating oil. Also, with respect to the amount of metalhydroxide charged, although as much as 25% may be used, large excessarnounts provide no particular advantage. Furthermore, the use of largeexcess amounts of the metal hydroxide reduces the fluidity of thereaction mass so that stirring of the reaction mixture and eventualfiltration are made more difficult. In instances where these latterdifficulties are encountered, however, theycan be overcome bythe-addition of adiluent solvent, such as benzene, toluene or the like,which is subsequently distilled from the final product.

The'oxidation time required 'to'incorporate the desired amount of metalinto the hydrocarbon reactant will, of course, vary depending upon theconditions employed, such as 'the equipment used, the rate of oxygen orair introduction, the temperature, the amount of metal hydroxidecharged, the type of hydrocarbon bei'ng oxidized, etc. As will be seenfrom the examples which follow, the oxidation times used varied fromabout 3 hours up to about 85 hours. From a practical standpoint, it is,of course, desirable to use oxidation equipment and conditions which areconducive to etfecting the oxidation to the desired extent in as short atime as possible. Accordingly, it is considered that modificationsdesigned to increase the efficiency of the oxidation procedure, such asthe use of oxidation catalysts and special reactors calculated to give amore efiicient disbursal of the oxidizing gas in the hydrocarbon, etc.,come within the broad purview of this invention.

Upon completion of the oxidation step the oxidized hydrocarbon productmixture may be filtered to remove the excess (unreacted) metal hydroxideand the phosphorus sulfide reagent added, or the phosphorus sulfide maybe added directly to the oxidized hydrocarbonmetal hydroxide reactionmixture. In conducting the reaction, from about 5% to about 20%, byweight (based on the weight of the hydrocarbon charge), of phosphorussulfide is added to the oxidized hydrocarbon product and the two mixedtogether. The mixture is then heated to a temperature of from about 75C. to about 150 C. for a suificient time to complete the reaction. Thereaction is usually complete in from about 10 minutes to about 10 hours.Although the temperature may be 'varied within the aforesaid rangewithout significantly effecting the final product, the highertemperatures, i. e., from about 125 C. to about 150 C. give productswhich are usually dark in color and which, therefore, tend to darken thecolor of the oils in which they are used. The lower temperatures,however, i. e., from about 75 C. to about 110 C., give lighter coloredproducts which provide better colored oil blends.

As will be seen from the examples, the metal contents of the ultimatecomplex salt products, on an undiluted basis, were increased from 1.94%for a charge of P 8 to 6.04% for a 15% charge on batches of the sameoxidized oil product. However, the sharpest rise in metal content occurswith the first 7.5% of the P 8 with only relatively slight increasesabove'that amount. The use of about of the phosphorus sulfide in thereaction is, therefore, considered to be the preferred amount to use.

The phosphorus contents of the finished products indicate that fromabout 70% to 100% of the phosphorus sulfide charged is reacted. However,the P/S ratio in the products ranges from 0.4 to 0.8 and for the mostpart averages about 0.6. This ratio is higher than 0.39 which is the P/Sratio in phosphorus pentasulfide, for example. It would appear then thatsome sulfur is lost in the reaction either as hydrogen sulfide or it isremoved as an oil-insoluble salt during the filtration step.

As mentioned previously, gelation of the reaction mixture is apt tooccur in the phosphorus sulfide reaction. This is paticularly so wherethe oxidized oil intermediate contains a relatively high percentage ofmetal, i. e., more than about 0.5%, and about 10%, or more of phosphorussulfide is added. Gelation does not usually occur when the reaction isconducted on the more mildly oxidized hydrocarbons, i. e., thosecontaining 0.5%, or less of metal. The gel formation, however, is in noWay harmful, and as afore-indicated, the gel is quickly broken by theaddition of water, which is added in all instances at this stage of theprocess.

In general with respect to the phosphorus sulfide reaction it can besaid that the use of a 10% charge of the phosphorus sulfide andconduction of the reaction at a temperature of from about 75 C. to about125 C. for about 1 hour using P 5 as the phosphorus sulfide reactant arethe preferred reaction conditions. It should be noted that somewhatlonger reaction times, i. e., 5 to 6 hours, are required for bestresults where P 8 is used as the sulfide reactant.

In this connection it has been found that both the phosphorusheptasulfide and the phosphorus trisulfide are not as reactive as thephosphorus pentasulfide under comparable conditions, the trisulfidegiving salt products having the lowest metal contents. However, the useof a triggering compound, such as sulfur, in conjunction with thesereagents substantially increases their reactivity and also increases themetal content of the ultimate products. The produt obtained using theP4S7S combination, for example, approaches that of the P 8 products inmetal content. Also, in the case of the P 8 .by extending the reactiontime to 5 or 6 hours, products may be obtained which are comparable tothe P 5 products without the use of sulfur. The amount of sulfur used inconjunction with the P 5 or P 8 should be about 10% to 25% based on thephosphorus sulfide used.

In conducting the reaction of the phosphorus sulfidetoxidizedhydrocarbon intermediate with the additional metal hydroxide in thepresence of water, the metal ghydroxide reagent can be either that whichis already present in thereaction mixture (if the mixture was notfiltered pior to the phosphorus sulfide reaction) or it can be a freshcharge of metal hydroxide. In any case, the amount of metal hydroxidepresent in the reaction mixture at this stage should be from about 2% toabout 25 (based on the original hydrocarbon charge) the usual amountbeing about 10%. The amount of water necessary is small, generally fromabout 2% to about 10% being suificient, although higher amounts may beused. The water is preferably added after cooling the reaction mixtureto a temperature below the boiling point of water, preferably to aboutC. Dehydration is then accomplished by heating the reaction mixtureabove the boiling point of water while passing a stream of nitrogentherethrough. The mixture is preferably heated to a temperature of fromabout 150 C. to about 200 C. and maintained at this temperature leveluntil all of the water is driven off. The product is generally filteredat or near this latter temperature level in order to obtain relativelyrapid filtration. Obviously, the dehydration may be accomplished inother ways, such as by adding a solvent, such as benzene, which may besubsequently distilled oif as an azeotropic mixture.

The metal hydroxides used in the water-treating and dehydration steps ofthe invention are the same as those utilized in the oxidation step, i.e., the hydroxides of the metals of groups I and II of the periodictable of the elements. However, the mixed metal salt products, i. e.,salt products containing more than one metal can be produced in theinvention by the use of one metal hydroxide in the oxidation step and adifierent metal hydroxide in the water-treating and dehydration steps,as is illustrated in the examples which follow.

A full understanding of the nature of the products of the invention andthe manner of their preparation may be had by reference to the followingspecific examples.

The oxidation step of the process is illustrated by Examples A to I.

EXAMPLE A a rate of 1.7 liters per hour per grams of oil for 85 hours.The introduction of air was then stopped and the reaction mixturestirred with 48 grams (4%) of Hyilo (a diatomaceous earth filter aid),filtered and cooled. The filtered product contained 1.49% calcium.

EXAMPLE B Two thousand grams of a percolated, solvent-refined,Mid-Continent type bright stock and 218 grams (11 weight percent) ofcalcium hydroxide were charged to an electrically heated column reactor,60 inches long by 3 inches in diameter, having a fritted glass piecesealed in the bottom. Sixty liters of air per hour were passed upthrough the oil, maintained at 204 C., for 24 hours. A portion of thereaction mixture was contacted with 4 weight percent of Hyflo andfiltered. Analysis showed the filtrate to contain 1.94% calcium. Thisexample illustrates the use of a column type reactor which provides amuch more eflicient use of the oxidizing gas than the flask type reactorused in Example A. Consequently, the oxidation time in this example isconsiderably shorter.

Additional oxidations were conducted (Examples C to J) following thesame general procedure employed in Example B, but varying the oxidationconditions. The pertinent data with respect to the several oxidationexamples are summarized in Table II.

.Tqble .II

- Percent Temper- Air-rate, -xida- Percent Example Hydrocarbon Stock,llrne ature, l./hr./ tlon Ca in charged C. 100 g. time, filtered 1 011hr. product A SOltvenKt-refinedMid-Continent type bright 7.2 190 1.785 1. 49

.s 00 B- do 11 204 3.0 24 1. 94 0. do. 1 21 218 5. 0' '27 2.84 D. do 10218 3.0 3 05-16 E- do 218 3. 0 7 0.57 F. do 10 218 3. 0 3 0.12 G- .do 3.7 190 2. 5 50 2. 23 H. Foots oi 7. 2 204 2.0 48 2. 14 I Slack wax 7.2190 1.7 50' 1.05 J Conventional 100 sec. at 100 F. paraflin oil- 10 2043. 0 .3 i 0. 1

; 521(011): was-charged instead of lime.

The following examples illustrate the reactionof oxidized hydrocarbonproducts, prepared in the manner illustrated by Examples A to K, withphosphorus sulfide and also the reaction of the products thus producedwith additional metal hydroxide in the presence of water to produce theproducts of the invention. The amount of EXAMPLE 1 Three hundred gramsof filtered, oxidized solventrefined, Mid-Continent type residual oilproduct containing 1.49% soluble calcium (Example A, Table II), dilutedwith 100 milliliters of xylene were charged into a 4-necked,round-bottomed flask equipped with a stirrer, thermometer and a gasinlet tube. This mixture was reacted with grams of P 8 (10%, by weight,of the oxidized oil product) at 130 *F..to 145 C. for A'hour in anatmosphere of nitrogen. .The mixture gelled. Two hundred milliliters oftoluene were added to reduce the viscosity. Seventy-five milliliters ofwater and 100 grams of limeuwere-added. The mixture was dehydrated to atemperature of 200 C. Five weight percent of Hyflo (filter aid) wasadded and the product filtered. The solvents were removed bydistillation.

Analyses:

Calcium percent 6.03 Phosphorus do 2.44 Sulfur do 3.79 Calcium increasedo 305 P 8 consumed do 88 13-10 stability No. 170

The percentage of additive, multiplied by 100, that reduces theN. N .-ofthe reference oil-t0 a value of.2. Thus, thelower the stability number,the more eifective the additive as an antioxidant.

EXAMPLE 2 One hundred and sixty-seven grams of a filtered, oxidized,solvent-refined, Mid Continent type residual oil product containing1.49% soluble calcium (Example A, Table-ll) were diluted with 100milliliters of xylene. This was reacted directly with 17 grams of P 8(10%) and 50 grams of lime at 140 C. to 150C. for 5 minutes. Thernixturebecame gelatinous. Another 200 milliliters of xylene-were added and themixture stirred for about 6 hours. After cooling to about 80 C. to 90C., 50 milliliters of water were carefully added. The gelatinous mixturebecame very fluid. The water was stripped up to 195 C. About 5%, byweight of Hyfio (filter aid) was added and the product filtered. Thesolvents were removed by distillation.

Analyses: Percent Calcium 6.5 Phosphorus 2.40 Sulfur 3.81 Calciumincrease 329 'P S ;consumed 86 Comparing Examples 1 and 2, it is seenthat the use of 6 hours reaction time and the addition of the lime alongwith the P 8 inExample Z, as compared to the A-hour reaction time usedin Example 1 did not. significantly affect the product in any way.

EXAMPLE 3 Analyses: Percent Calcium 1 2.25 Phosphorus 0.75 Sulfur 1.49Calcium increase 132 P 8 consumed 1 4.50% on undiluted basis.

EXAMPLE 4 This example is the same as Example 3 with the exception that15 grams ofl S (7.5%, by weight, of the calcium oxidized residual oilproduct) were used.

Analyses: Percent Calcium 1 2.78 Phosphorus 1.02 Sulfur 1.90 Calciumincrease 187 P 8 consumed 98 1 5.56% on undiluted basis.

EXAMPLE 5 This example is the same as Example 3 with the exception the20 grams of P S 10%, by weight, of the calcium oxidized residual oilproduct) were used.

This example is the same as described in Example 3 with the exceptionthat 30 grams of P S (15%, by weight, of calcium oxidized residual oilproduct) were used. A gel formed after 12 minutes reaction time. A smallamount of water (about 2% by weight) broke the gel and restored theoriginal fluidity.

Analyses: Percent Calcium 1 3.02 Phosphorus 1.84 Sulfur 3.04 Calciumincrease 211 P 5 consumed 88 1 6.04% on undiluted basis.

Examples 3 to 6 show the increase in metal content of the complex saltproduct attained by increasing the amount of P 5 used from 5% to 7.5% toand to respectively. The sharpest rise, however, occurs with the first7.5% of P 8 with more gradual increases being obtained with 10% and 15%of the P S EXAMPLE 7 Two hundred and seventy-seven grams of anunfiltered, oxidized, solvent-refined, Mid-Continent residual oilproduct-lime mixture containing 1.27% calcium (prepared after thefashion of Example B, Table II) and 125 grams of conventional parafiinoil (300 seconds of 100 F.) were reacted with 25 grams of P 8 (about10%, by weight, of the calcium oxidized residual oil product) at 100 C.to 110 C. for 3 hours in an atmosphere of nitrogen. Twenty-fivemilliliters of water (10%) were slowly added at 80 C. No additional limewas added over and above that which was present in the original mixture.ture of 190 C. Four weight percent of Hyfio (filter aid) was added andthe product filtered.

1 3.81% on undiluted basis.

EXAMPLE 8 Two hundred grams of a filtered, oxidized, solventrefinedMid-Continent type residual oil product containing 2.84% barium (ExampleC, Table II) were diluted with 200 grams of 100 seconds Mid-Continentoil. This was reacted with grams of P 8 (10%) at 140 C. to 150 C. for 1hour in an atmosphere of nitrogen. Twenty milliliters of water werecarefully added at 90 C. followed by the addition of 85 grams of bariumhydroxide (dry). The total mixture was dehydrated up to a temperature of190 C. Eight weight percent of Hyfio (filter aid) was added and theproduct filtered.

Analyses: Percent Barium 1 7.9 Phosphorus 1.30 Sulfur 2.14 Bariumincrease 460 P 3 consumed 97 1 15.8% on undiluted basis.

The mixture was dehydrated up to a tempera- 10' This example illustratesthe application of the process to a barium-oxidized oil using bariumhydroxide as the water-complexing reagent.

EXAMPLE 9 Four hundred grams of an unfiltered, oxidized, Mid- Continentresidual oil product (0.16% calicum)-lirne mixture (Example D, Table II)and 40 grams of P 8 were reacted in equipment described in Example 1 at140 C. to 150 C. for 1 hour in an atmosphere of nitrogen. After coolingto 80 C. to C., 40 milliliters of H 0 and 80 grams of lime were added.The mixture was slowly dehydrated to 190 C. Eight weight percent ofHyfio (filter aid) was added and the product filtered immediately.

Analyses Percent Calcium 3 .87 Phosphorus 2.14 Sulfur 3.38 P 8 consumed85 Calcium increase 2,300

This example shows the applicability of the process of the invention toa mildly oxidized oil (0.16% calcium)- EXAMPLE 10 Example 9 wasduplicated with an unfiltered, oxidized, residual oil product containing0.12% calcium (Example F, Table II).

Analyses:

Calcium percent 2.83 Phosphorus do 1.97 Sulfur do 3.00 3-10 stabilityNo. 190

EXAMPLE Example 10 was duplicated except that the batch size wasincreased five-fold.

Analyses:

Calcium percent 2.78 Phosphorus do 1.89 Sulfur do 2.88 13-10 stabilityNo 185 EXAMPLE 10b Example 10a was duplicated.

Analyses: Percent Calcium 2.79 Phosphorus 1.86 Sulfur 2.85

Examples 10, 10a and 10b show the reproduceability of the products ofthe process.

EXAMPLE 106 Analyses:

Calcium percent 0.1 1 Barium do 10.30 Phosphorus do. 2.09 Sulfur do 2.24B-10 stability No Ca P 8 consumed percent 85 This example illustratesthe production of a mixed metal salt of calcium and barium by the use ofcalcium.

woe-

11 hydroxide in the oxidation step and barium hydroxide ie'i hs a -e mains st p- EXAMPLE 11 Four hundred grams of an unfiltered, oxidized,residual oil product containing 0.16% calcium (prepared in the manner ofExample F, Table II) and 30 grams of P 8 were reacted for 1 hour at 140C. to 150 C. Twenty grams of lime were added in the absence of water.The temperature was raised to 190C. Four weight percent of Hyflo (filteraid) was added and the product filtered immediately.

Analyses: Percent Calcium 0.06 Phosphorus 0.98 Sulfur 3.45

The poor metal content of this product shows the necessity for havingwater present in the reaction of the oxidized oil-P 8 product with theadditional metal hydroxide.

EXAMPLE 12 Four hundred grams of an unfiltered, calcium oxidizedresidual oil mixture containing 0.57% calcium (Example E, Table II) and40 grains of P S were reacted in equipment described in Example 1 at 140C. to 150 C. for 1 hour in an atmosphere of nitrogen. After cooling to80 C. to 90 C., 40 milliliters of water and 40 grams of lime were added.The mixture was slowly dehydrated to 190 C. Four weight percent of Hyflo(filter aid) was added and the product filtered.

Analyses: Percent Calcium 4.64 Phosphorus 2.47 Sulfur 4.29 P S consumed90 EXAMPLE 13 One hundred grams of a filtered, calcium-oxidized residualoil product containing 2.76% calcium (same as Example B, Table II,except oxidization time was 30 hours) were diluted with 150 grams ofconventional paraffin oil (100 seconds at 100 F.). This was reacted with10 grams (10%) of lime and 10 grams of P 8 in equipment described inExample 1 at 140 C. to 155 C. for 1% hours in an atmosphere of nitrogen.A heavy geT-formed when the mixture was cooled to 80 C. The

gel broke when 20 milliliters of water and 20 grams of lime were added.The mixture was slowly dehydrated to 190 C. Eight weight percent of-Hyfio (filter aid) was added and the product filtered.

Analyses Percent Calcium 1 2.24 Phosphorus 1.15 Sulfur 1.98

1 5.6% on undiluted basis.

EXAMPLE 14 Analyses 7 Percent Calcium 2.72 Phosphorus 1.61 Sulfur 1.76

1 on undiluted basis.

EXAMPLE 15 Two hundred grams of a filtered, oxidized, solvent-refined,Mid-Continent type distillate oil product containing 2.23% solublecalcium (Example G, Table II) were dilutedwith 200 grams of conventionalparaflin oil (100 seconds at 100 'F.). This was charged to equipmentdescribed in Example 1 and reacted with 20 grams of P 5 (10%, by Weight,of the calcium oxidized distillate oil product) at 140 C. to 150 C. inan atmosphere of nitrogen. A gel formed after 5 minutes reaction time.Twenty milliliters of water were carefully added at C. followed by theaddition of 20 grams of lime. The mixture was dehydrated up to atemperature of 190 C. Four weight percent of Hyfio (filter aid) wasadded and the product filtered.

Analyses Percent Calcium 1 2.43

Phosphorus 1.22 Sulfur 1.78

Calcium increase 118 P 5 consumed 91 1 4.86% on undiluted basis.

EXAMPLE 16 Two hundred grams of a filtered, oxidized, foots oil productcontaining 2.14% soluble calcium (Example H, Table II) were diluted with200 grams of conventional parafiin oil (100 seconds at 100 F.). This wascharged to equipment described in Example 1 and reacted with 20 grams ofP 8 (10%, by weight, of the calcium-oxidized distillate wax product) at140 C. to 150 C. for /2 hour in an atmosphere of nitrogen. Twentymilliliters of water were carefully added followed by the addition of 20grams of lime. The mixture was dehydrated up to a temperature of 190 C.Four weight percent of Hyflo (filter aid) was added and the productfiltered.

Analyses: Percent Calcium 1 2.68 Phosphorus 1.26 Sulfur 1.84 Calciumincrease 150 P 5 consumed 95 1 5.36% on undiluted basis.

EXAMPLE 17 Two hundred grams of a filtered, oxidized, slack wax productcontaining 1.08% soluble calcium (Example I, Table II) were diluted with300 grams of conventional paratfin oil seconds at 100 F.) This wascharged to equipment described in Example 1 and reacted with 20 grams ofP 5 (10%, by Weight, of the calcium oxidized residual wax product) at C.to C. for 1V2 hours in an atmosphere of nitrogen. Twenty milliliters ofwater were carefully added followed by the addition of 40 grams of lime.The mixture was dehydrated up to a temperature of C. Four weight percentof Hyflo (filter aid) was added and the product filtered.

Analyses: Percent Calcium 1 1.71 Phosphorus 1.06 Sulfur 1.36 Calciumincrease 138 P 5 consumed 98 1 2.57% on undiluted basis.

EXAMPLE 18 Twenty-one hundred and fifty grams of an unfiltered,calcium-oxidized wax benzene (2-12) product containing 0.12% oil-solublecalcium metal (prepared under the conditions of Example F, Table II)were reacted with For preparation see U. s. Patent No. 2,476,972.

Analyses:

Calcium percent 2.53 Phosphorus do 1.37 Sulfur d 2.17 B-10 stability No175 EXAMPLE 19 Four hundred and forty grams of an unfiltered mixture ofcalcium-oxidized dodecylbenzene residue 1 containing This is the highboiling residue from dodecylbenzene manufacture.

0.13% oil-soluble calcium metal (prepared after the fashion of ExampleK, Table II) were reacted with 40 grams of phosphorus pentasulfide (10%,by weight, of oil) under an atmosphere of nitrogen at 140 C. to 145 C.for 3 hours (equipment used is described in Example 1). The mixture wascooled to 80 C. to 90 C. Forty milliliters of water were carefullyadded. The mixture was dehydrated up to a temperature of 190 C. Twentygrams (5 by weight) of Hyfio (filter aid) were EXAMPLE 20 Four hundredand forty grams of anunfiltered, calcium-oxidized white oil product(Nujol) containing 0.21% oil-soluble calcium metal and 1.46% oxygen(prepared under the conditions of Example F, Table II) were reacted with40 grams of phosphorus pentasulfide by weight, of oil) for 3 hours at150 C. in an atmosphere of nitrogen. The mixture was cooled to 80 C. to90 C. Fourty milliliters of water were carefully added followed by 40grams of lime. The mixture was dehydrated up to 150 C. Twenty grams (5%,by weight) of Hyflo (filter aid) were added and the mixture filteredhot.

Analyses Percent Calcium 3.51 Phosphorus 2.13 Sulfur 3.52

Examples to show the use of several difierent types of hydrocarbonreactants in the process of the invention.

EXAMPLE 21 Analyses:

Calcium percent 1.99 Phosphorus do- 1.98 Sulfur do 2.25 B-10 stabilityNo B-10A stability No. 24 hours 500 EXAMPLE 22 Example 21 was duplicatedexcept that after the phosphorus heptasulfide was rapidly added, 5 gramsof sulfur were slowly added over about 1 hour. The mixture was heated at150 C. for an additional 2 hours. The final steps were the same as inExample 21.

Analyses:

Calcium percent. 2.76 Phosphorus o 2.28 Sulfur d 2.75 B-10A stabilityNo., 24 hours 430 EXAMPLE 23 Example 21 was duplicated with theexception that 40 grams of phosphorus trisulfide (P 5 were used.

Analyses: Percent Calcium 0.70 Phosphorus 0.62 Sulfur 1.18

EXAMPLE 24:

Example 22 was duplicated except that 40 grams of phosphorus trisulfidewere substituted for phosphorus heptasulfide.

EXAMPLE 25 A mixture of pounds of Mid-Continent type bright stock and 10pounds of lime were air oxidized (1.5 cu. ft./min.) in a conical shapedsteel container at 400 F. for 5 hours. The oxygen content of a filteredsample of oxidized oil was 2.08%.

The unfiltered oxidized oil-lime mixture was transferred to a 30-gallonglass-lined Pfaudler kettle and treated with 7.5 pounds of P 8, (7.5%,by weight, of oxidized oil) at 220 F. for 6 hours in a nitrogenatmosphere. The mixture was cooled to 160 F. to 170 F. Ten pounds ofwater (10%) were added portionwise over 1 hour. After an additional 10pounds of lime (10%) were added to complete the final neutralization,the water was removed over a 3-hour period up to a temperature of 150 C.Ten pounds of Hyde (filter aid) were added to facilitate filtrationthrough a conventional plate and frame filter press.

Examples 21 to 26 illustrate the use of phosphorus heptasulfide andphosphorus trisulfide in the process of the invention. It will be seenthat these sulfides provide products having metal contents somewhatlower than products prepared using phosphorus pentasulfide (compareExamples 21 and 23 with Example 9). However, the use of sulfur as atriggering agent in conjunction with, with the P 8 and P 8 increased themetal contents of the ultimate products (compare Examples 22 and 24 withExamples 21 and 23, respectively). Example 25- shows that by extendingthe reaction time from 3 hours (Example 21) to six hours, the metalcontent of the P 5 product was greatly increased.

EXAMPLE 26 Four hundred grams of a filtered, calcium-oxidized,Mid-Continent residual oil product containing 0.16% oilsoluble calciummetal (prepared under the conditions of Example D, Table II) werereacted with 40 grams of phosphorus pentasulfide for one hour at C. toC. in an atmosphere of nitrogen. The mixture was cooled- (4%, byweight), of Hyflo (filter aid) were added and the mixture filtered hot.

EXAMPLE 27 Four hundred grams of a filtered, calcium-oxidized,Mid-Continent residual oil product containing 0.12% oilsoluble calciummetal (for oxidation conditions see Example F, Table II) were reactedwith 30 grams of phosphd ruspentasulfide (7.5%)for 3 hours at 170 C. inan atmosphere of nitrogen. One-half of the mixture was filtered.

An l e Neutralization No 16 (1st break). 24 (1st break). Phosphorus 2.07percent. Sulfur 4.13 percent. B-10 stability No 47.

Analyses:

Zinc percent 1.20 Phosphorus do 1.77 Sulfur do 3.22 B-lO stability No175 EXAMPLE 28 Four hundred grams of a filtered, Mid-Continent type,

calcium-oxidized residual oil product containing 0.25% 7 oil-solublecalcium metal and 1.20% oxygen (for oxidation conditions see Example F,Table II) were reacted with 40 grams of phosphorus pentasulfide (10%, byweight, of oil) for 3 hours at 150 C. in an atmosphere of nitrogen. Themixture was cooled to 80 C. to 90 C. Twenty milliliters of water werecarefully added followed by a solution containing 16 grams of NaOH in 20milliliters of water. The mixture was dehydrated up to 150 C. Onehundred grams of this product were removed and filtered.

Analyses:

Calcium percent 0.20 Sodium ..do 2.30 Phosphorus do 2.50 Sulfur do 3.63BaseNumber 8.9 B-10A stability No 200 EXAMPLE 29 To the remainder of theproduct from Example 28, a solution containing 27 grams of ZnCl in 60milliliters of water was added. The mixture was dehydrated up to 160 C.Fifteen grams (5%, by weight,) of Hyflo (filter aid) were added and theproduct filtered hot.

Analyses: Zinc i percent 3.34 Calcium do.. 0.20 Sodium do 2.02Phosphorus do 2.24 Sulfur do 2.99 Chlorine do 3.84 B-10A stability No600 Examples 26 to 28 illustrate the use of zinc carbonate,

zinc oxide and sodium hydroxide, respectively, as metal salt reagents inthe water-complexing step, while Example 29 shows the further complexingof the sodium hydroxide-complexed product with zinc chloride. It will beseen from the latter example that the reaction which occurs is acomplexing of the zinc chloride with the sodium salt, rather than ametathetical exchange which would ordinarily occur by a reaction of asodium salt with zinc chloride.

EXAMPLE so A mixture of two thousand grams of a Mid-Continent typeresidual oil and 100 grams of zinc oxide (5%, by weight,) were airoxidized at 420 F. for 3 /2 hours with an air rate equivalent to 3 l./100 grams of oil/hour.

Four hundred and twenty grams of this mixture containing 0.09%oil-soluble zinc metal and 0.70% oxygen were reacted with 40 grams ofphosphorus pentasulfide at 150 C. for 3 hours in an atmosphere ofnitrogen. The mixture was cooled to C. to C. and forty milliliters ofwater were carefully added. The mixture was dehydrated up to 150 C.Twenty grams of Hyflo (filter aid) were added and the mixture filteredhot.

(a) A sodium-oxidized residual oil intermediate was made by oxidizing a3.5% caustic soda in oil mixture at 218 C. with an air rate equivalentto 5 l./hr./ grams of oil. The oxygen and oil-soluble sodium contents ofthe oxidized product were 1.42% and 0.7%, respectively.

(b) Four hundred grams of the unfiltered sodium-oxidized residualoil-caustic soda mixture (a) were reacted with 30 grams of P487 (7.5weight percent) for six hours at C. in a nitrogen atmosphere. Aftercooling the mixture to 80 C., 40 milliliters of water were carefullyadded followed by 40 grams of lime. The mixture was dehydrated to atemperature of 150 C. Five percent of Hyflo (filter aid) was added andthe mixture filtered.

31(a), with the exception that 40 grams of P S (10 weight percent) weresubstituted for the P 8 and reacted for three hours.

Analyses:

Calcium percent 2.62 Sodium do i 0.7 Phosphorus do 2.30 Sulfur 7 o 2.68B-10 stability No.

17 EXAMPLE 33 Four hundred grams of an unfiltered sodium-oxidizedresidual oil-caustic soda mixture containing 0.87% oxygen and 0.5%oil-soluble sodium were reacted with 40 grams of P 8 weight percent) for4 hours at 105 C. in a nitrogen atmosphere. After cooling the mixture to80 C., 20 milliliters of water were carefully added followed by asolution of 40 grams of caustic soda in 60 milliliters of water. Themixture was dehydrated to a temperature of 200 C. Five percent ofStandard Super Cel (filter aid) was added and the mixture filtered.

Analyses: Percent Sodium 3.70 Phosphorus 1.82 Sulfur 2.2.0

Example 30 illustrates the use of zinc oxide in the oxidation andwater-complexing steps of the invention. Examples 31 and 32, on theother hand, show the use of sodium hydroxide in the oxidation step withP 3 as the phosphorus sulfide reactant in one case (Example 31) and P 5in another (Example 32), the water-complexing salt being calciumhydroxide. Example 33 shows the use of sodium hydroxide in both theoxidation and watercomplexing steps.

EVALUATION OF PRODUCTS Table IV Calcium L-l caterpillar test Prod- Gone,in oil uct percent blend, 5 added percent Test Piston Lacquer Percenttune, hr rating demerits TGI N 0ne 120 61. 9 28. 2 6 Do 120 57.4 =31.0 7120 98. 8 e 0.7 0 10 X 4. 0 0.11 240 97. 6 a 1.4 1 480 94.3 B g 120 99.X 1 4. 0 0.11 2 1 3 1 0 Y 2.8 0.11 240 3% i i 240 9 Y 2 088 i 480 93. 9a. 9 5 120 99. 3 I 0.0 4 Z 2. 9 0. 088 240 98. 3 f 0. 1 13 480 97.1 1 0.8 120 99. 7 B 0. 1 1 Z 2. 9 0.088 240 99. 0 B 0. 4 6 480 93. 2 s 4. 2 12X-A product similar to that described in Ex. 10a; ca1cium=2.79%;phosphorus=1.86%; sulfur=2.85%.

YA product similar to that described in Ex. 12, except 15% P255 wasused; calciu1n=4.02; phosphorus=2.56%; sulfur=2.62%.

Z-A pilot plant batch of a product similar to X. Calc1um=3.07%;phosphorus=1.93%; suliu.r=3.58%.

Ba.se oil is an SAE grade solvent-refined Mid-Oontment 011, K. V. at 210F.=11.08 05., K. V. at 100 F.=101.4 cs.

B1end also contained 0.5% of a commercial antioxidant (a pmene-PzSreaction product).

Blend also contained 0.25% of a commercial antioxidant as m footnoteBlend also contained 0.5% of a commercial antioxidant (a suliurized terene -Blend also contained 0.5% of a commercial antioxidant (zinc di- 30hexyldith iophosphate). The ability of the reaction products of theinvention TGILDOP Grove Packmg' as detergents and antioxidants forengine lubricating oils LAUSON ENGINE D-4A TEST has been demoflfitratedy subjecting Oil blends of 01656 This test determines the effectivenessof the lubricatproducts to engme tests. The detergent tests used were iil i preventing piston fouling a measured by the the Lauson (11693113-21, R diesel 13-23 cleanliness of the rings, lands, grooves andpiston skirts. and caterplllar ellglne tests- The antlOXldaIlt ieSiSCleanliness ratings are assigned at the end of the test were the LausonD4{& and 08-2 tests. The several tes on a le f f m 100 to O, a 100rating signifying procedures are described below. The results obtained aperfectly clean condition and a zero rating represent- III arepresentatlve numbfif of tests are 5 1n Tablfis ing the worst possibledeposit condition. Bearing weight III and IV. From these test results itis apparent that 40 l i l o measured as supplemental data. A single theproducts of the invention are outstanding detergents cylinder, 4-cyc1e,liquid-cooled Lauson engine with splash for engine lubricating oils whenused either alone or in l bri ation and having a copper-lead bearing isemployed combination with known antioxidants. Also, it is seen i thetest. The operating conditions are as follows: that the productsprepared from the mildly oxidized oils, Sample "gallon" 1 1. e., thosehaving less than 0.5% metal contents, are Oil temperature 225 the bestdetergents (see Examples 9 and 10a, Table III). J ket temperature P 275The data in Table III also show that the products of the Speed R. P. M1825 invention are efl'ective antioxidants, particularly those Brakeload H P 1.6 produced from the mildly oxidized oil intermediates.One-half throttle air-fuel ratio 13-1 Table III Lauson D4A engine B CFRD-21 OFR D-23 Lauson OS2 engine B diesel b diesel b Percent ProductMetal, Percent Percent Inetalin added percent phossulfur oxidized phorusPercent Avg.% Percent Percent Percent AvgJA oil interproduct Rating brg.wt. product Rating product Rating product Rating brg. wt. mediate loss,mg. loss, mg.

None None. Ex. 2 Ex. 8---- Ex. 9..-. Ex. 10a.- Ex. 1%.. Ex. l0c Ex.12-.. Ex. 15 Ex. 16... 1. 26 2.14 Ex. 17..- Oa1.71 1.06 1.08

e The base oil was an SAE oil blend equivalent to 0.3% Ba (0.088% Ca),except where noted 20 grade solvent-refined, Pennsylvania oil (kin. vis.at F.=63 es.; kin. vls. at 210 F.=8.3 05.). Metal content of b The baseoil was an SAE 30 grade solvent-refined, Mid-Continent oil (kin. vis. at100 F.==121 cs.; kin. vis. at 210 F.=l2.2 03.). Metal content of oilblend equivalent to 0.3% Ba (0.088% Ca).

0 The oil blend also contained 0.5% of a commercial antioxidant(pinene-PrSi product),

P1 The oil contained 1.0% of the commercial antioxidant as in 12357,,more additive was used.

19 Oil was added every 20 hours. The duration of the test is 100 hours.The piston cleanliness rating and the bearing Weight loss obtained withthe test oil is compared to that obtained with the reference oil.

CFR DIESEL DETERGENCY TEST D21 This test determines the effectiveness ofthe lubricating oil in preventing piston deposits and top ring wear. Asingle cylinder, CFR 4-cycle, supercharged diesel engine is used. Theoperating conditions are as follows:

Oil temperature F 175 Jacket temperature F 212 Speed R. P. M 1800 Brakeload "H. P 7.5

I A one and one-half gallon sample of oil is used with addition of oilevery 8 hours starting at 4 hours. The duration of the test is 60 hours.The diesel fuel used contained 1% sulfur. The results of the test arereported in terms of piston cleanliness ratings as in the D-4A test.

CFR DIESEL DETERGENCY TEST D23 This test determines the effectiveness ofan oil in preventing piston deposits and top ring wear. The operatingconditions are as follows:

Oil temperature F 175 Jacket temperature F 212 Speed R. P. M 1800 Brakeload H. P 4.5

A one and one-half gallon sample of oil is used at the start and oil isadded every 8 hours starting at 4 hours. The duration of the test is 60hours. The diesel fuel used contained 0.4% sulfur. The results are givenin terms of piston cleanliness ratings using the same rating system asin the Lauson D-4A and diesel D-2l test.

CRC CATERPILLAR ENGINE TEST L-l This is a specification engine test todetermine the ability of an oil to prevent engine deposits including thepiston and crankcase deposits. A single cylinder, 4-cycle caterpillarengine is used. The operating conditions are as follows:

011 temperature F 150 Jacket temperature F 180 Speed -R. P. M 1000 Brakeload H. P 19.8

Twenty gallons of oil is used in the engine at the start of the test andthe oil is changed at 120-hour intervals. The duration of the test is480 hours. The diesel fuel used contained 0.4% sulfur. The condition ofthe engine at the end of the test is expressed by an engine cleanlinessrating based on a scale from to 100, 100 being a perfectly clean engine.

It will be appreciated that the products of this invention are actuallyoil solutions of the phosphorus-, sulfurand metal-containing oxidizedoil products, and although the products shown in the examples presentedherein vary with respect to the concentration of the products in theoil, it will be understood that these differences can be eliminated bystandardization of process proce- 20 sants, viscosity index improvers,defoamants, rust preventives, etc.

Although the invention has been described herein by means of certainspecific embodiments and illustrative examples, it is not intended thatit be limited in any way thereby, but only as indicated in theaccompanying claims.

What is claimed is:

1. An oil-soluble, phosphorus-, sulfurand metal-eontaining oxidizedhydrocarbon reaction product produced by the method which comprises thesteps of (1) forming a mixture comprising (a) a hydrocarbon having amolecular weight of from about 200 to 1000 and which is selected fromthe group consisting of aliphatic hydrocarbons and aromatic hydrocarbonshaving at least one nuclear hydrogen atom substituted by an aliphaticradical to provide a total of at least 8 aliphatic carbon atoms permolecule therein, and mixtures thereof, and (b) from about 0.5% to about25%, based on the weight of said hydrocanbon, of a metal hydroxide, themetal constituent of which is selected from Groups I and II ofMendeleeffs Periodic Table of the Elements, (2) contacting said mixturewith an oxidizing gas at a temperature of from about 125 C. to about 325C. to effect oxidation of said hydrocarbon and reaction of said metalhydroxide with the oxidized hydrocarbon, (3) continuing the oxidationfor a time suflicient to incorporate from about 0.05% to about 3.0%, byweight, of metal into the oxidized hydrocarbon, (4) reacting the productfrom step 3 with from about 5% to about 20%, by weight, based on theweight of hydrocarbon charged in step 1, of a phosphorus sulfide, at atemperature of from about C. to about 150 C., to form a phosphorus,sulfurand metal-containing product, (5) providing a mixture of thereaction product from step 4 with from about 2% to about 25 by weight,based on the hydrocarbon charged in step 1, of a metal hydroxide, themetal constituent of which is selected from Groups I and II ofMendeleetts Periodic Table of the Elements, and water, at a temperaturebelow the boiling point of water, (6) substantially completelydehydrating the mixture formed in step 5 and (7) subjecting thedehydrated mixture to filtration to remove insolubles therefrom.

2. An oil-soluble, phosphorus, sulfurand metal-containing oxidized oilreaction product produced by the method which comprises the steps of (1)forming a mixture comprising (a) a petroleum oil having a molecularweight of from about 200 to about 1000 and (b) from about 0.5 to about25%, based on the weight of said oil, of a metal hydroxide, the metalconstituent of which is selected from Group II of Mendeleetfs PeriodicTable of the Elements, (2) contacting said mixture with an oxidizing gasat a temperature of from about C. to about 325 C. to effect oxidation ofsaid oil and reaction of said metal hydroxide with the oxidized oil, (3)continuing the oxidation for a time sufiieient to incorporate from about0.05 to about 3.0%, by weight, of metal into the oxidized oil, (4)reacting the product of step 3 with from about 5% to about 20%, byweight, based on the oil charged in step 1, of a phosphorus sulfide, ata temperature of from about 75 C. to about dure and also when requiredby distillation of a portion 7 C., to form a phosphorus-, sulfurandmetal-containing product, (5) providing a mixture of the reactionproduct from step 4 with from about 2% to about 25 I by weight, based onthe oil charged in step 1, of a hydroxide of a metal selected from GroupII of Mendeleeffs .Periodic Table of the Elements, and water, at atemperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

3. An oil-soluble, phosphorus-, sulfurand calciumcontaining oxidized oilreaction product produced by the method which comprises the steps of (1)forming a mixture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5% to about25% of calcium hydroxide, (2) contacting said mixture with an oxidizinggas at a temperature of from about 125 C. to about 325 C. to effectoxidation of said oil and reaction of said calcium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufficient toincorporate from about 0.05 to about 3.0%, by weight, of calcium intothe oxidized oil, (4) reacting the product from step 3 with from aboutto about by weight, based on the hydrocarbon charged in step 1, of aphosphorus sulfide, at a temperature of from about 75 C. to about 150C., to form a phosphorus-, sulfurand calcium-containing product, (5)providing a mixture of the reaction product from step 4 with from about2% to about by Weight, based on the weight of the oil charged in step 1,of calcium hydroxide, and water, at a temperature below the boilingpoint of water, (6) substantially completely dehydrating the mixtureformed in step 5 and (7) subjecting the dehydrated mixture to filtrationto remove insolubles therefrom.

4. An oil-soluble, phosphorus-, sulfurand calciiuncontaining oxidizedoil reaction product produced by the method which comprises the steps of(1) forming a mixture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5 to about25 based on the weight of said oil, of calcium hydroxide, (2) contactingsaid mixture with an oxidizing gas, at a temperature of from about 125C. to about 325 C., to effect oxidation of said oil and reaction of saidcalcium hydroxide with the oxidized oil, (3) continuing the oxidationfor a time sufiicient to incorporate from about 0.05% to about 0.5%, byweight, of calcium into the oxidized oil, (4) reacting the product fromstep 3 with from about 5% to about 20%, by weight, based on the weightof oil charged in step 1, of phosphorus pentasulfide, at a temperatureof from about 75 C. to about 150 C. to form a phosphorus-, sulfurandcalcium-containing product, (5 providing a mixture of the reactionproduct from step 4 with from about 2% to about 25%, by weight, based onthe weight of oil charged in step- 1 of calcium hydroxide, and water, ata temperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

5. An oil-soluble, phosphorus-, sulfurand bariumcontaining oxidized oilreaction product produced by the method which comprises the steps of (1)forming a mixture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5 to about25 based on the weight of said oil, of barium hydroxide, (2) contactingsaid mixture with an oxidizing gas, at a temperature of from about 125C. to about 325 C., to efiect oxidation of said oil and reaction of saidbarium hydroxide with the oxidized oil, (3) continuing the oxidation fora time sufiicient to incorporate from about 0.05% to about 3.0%, byweight, of barium into the oxidized oil, (41) reacting the product fromstep 3 with from about 5% to about 20%, by weight, based on the weightof the oil charged in step 1, of a phosphorus sulfide, at a temperatureof from about 75 C. to about 150 C., to form a phosphorus-, sulfurandbarium-containing product, (5) providing a mixture of the reactionproduct from step 4 with from about 2% to about 25%, by weight, based onthe weight of the oil charged in step 1, of barium hydroxide, and water,at a temperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

6. An oil-soluble, phosphorus-, sulfurand barium-com taining oxidizedoil reaction product produced by the method which comprises the steps of(1) forming a mix ture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5 to about25 based on the weight of said oil, of barium hydroxide, (2) contactingsaid mixture with an oxidizing gas, at a temperature of from about 125C. to about 325 C., to effect oxidation of said oil and reaction of saidbarium hydroxide With the oxidized oil, (3) continuing the oxidation fora time sufficient to incorporate from about 0.05% to 0.5%, by weight, ofbarium into the oxidized oil, (4) reacting the product from step 3 withfrom about 5% to about 20%, by weight, based on the Weight of the oilcharged in step 1, of phosphorus pentasulfide, at a temperature of fromabout C. to about 150 C., to form a phosphorus-, sulfurandbarium-containing product, (5) providing a mixture of the reactionproduct from step 4 with from about 2% to about 25%, by weight, based onthe weight of oil charged in step 1, of barium hydroxide, and water, ata temperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

7. An oil-soluble, phosphorus-, sulfur-, calciumand zinc-containingoxidized oil reaction product produced by the method which comprises thesteps of (l) forming a mixture comprising (a) a petroleum oil having amolecular weight of from about 600 to about 1000 and (b) from about 0.5%to about 25%, based on the weight of said oil, of calcium hydroxide, (2)contacting said mixture with an oxidizing gas at a temperature of fromabout 125 C. to about 325 C. to effect oxidation of said oil andreaction of said calcium hydroxide with the oxidized oil, (3) continuingthe oxidation for a time sufficient to incorporate from about 0.05% toabout 3.0%, by weight, of calcium into the oxidized oil, (4) reactingthe product from step 3 with from about 5% to about 20%, by weight,based on the weight of oil charged in step 1, of a phosphorus sulfide ata temperature of from about C. to about 150 C. to form a phosphorus-,sulfurand calcium-containing product, (5) providing a mixture of thereaction product from step 4 with zinc hydroxide and water at atemperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

8. An oil-soluble, phosphorus-, sulfur-, calciumand zinc-containingoxidized oil reaction product produced by the method which comprises thesteps of (l) forming a mixture comprising (a) a petroleum oii having amolecular weight of from about 600 to about 1000 and (b) from about 0.5%to about 25 based on the weight of said oil, of calcium hydroxide, (2)contacting said mixture with an oxidizing gas, at a temperature of fromabout C. to about 325 C., to efiect oxidation of said oil and reactionof said calcium hydroxide with the oxidized oil, (3) continuing theoxidation for a time sufiicient to incorporate from about 0.05% to 0.5%,by Weight, of metal into the oxidized oil, (4) reacting the product fromstep 3 with from about 5% to about 20%, by weight, based on the weightof oil charged in step 1, of phosphorus pentasulfide, at a temperatureof from about 75 C. to about C., to form a phosphorus-, sulfurandcalcium-containing product, (5) providing a mixture of the reactionproduct from step 4 with from about 2% to about 25%, based on the weightof the oil charged in step 1, of zinc hydroxide, and water, at atemperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

9. An oil-soluble, phosphorus, sulfurand calciumcontaining oxidized oilreaction product produced by the method which comprises the steps of (1)forming a mix- 23 ture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5% to about25% of calcium hydroxide, (2) contacting said mixture with an oxidizinggas, at a temperature of from about 125 C. to about 325 C., to effectoxidation of said oil and reaction of said calcium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufiicient toincorporate from about 0.05% to about 0.5 by weight, of calcium into theoxidized oil. (4) reacting the product from step 3 with from about toabout by weight, based on the weight of oil charged in step 1, ofphosphorus heptasulfide, at a temperature of from about 75 C. to about150 C., to form a phosphorus, sulfurand calcium-containing product, (5)providing a mixture of the reaction product from step 4 with from about2% to about by weight, based on the weight of oil charged in step 1, ofcalcium hydroxide, and water, at a temperature below the boiling pointof water, (6) substantially completely dehydrating the mixture formed instep 5 and (7) subjecting the dehydrated mixture to filtration to removeinsolubles therefrom.

10. An oil-soluble, phosphorus-, sulfurand calciumcontaining oxidizedoil reaction product produced by the method which comprises the steps of(1) forming a mixture comprising (a) a petroleum oil having a molecularweight of from about 600 to about 1000 and (b) from about 0.5 to about25 of calcium hydroxide, (2) contacting said mixture with an oxidizinggas, at a temperature of from about 125 C. to about 325 C., to effectoxidation of said oil and reaction of said calcium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufficient toincorporate from about 0.05 to about 0.5 by weight, of calcium into theoxidized oil, (4) reacting the product of step 3 with from about 5% toabout 20%, by weight, based on the weight of the oil charged in step 1,of phosphorus trisulfide, at a temperature of from about 75 C. to about125 C., to form a phosphorus-, sulfurand calcium-containing product, (5)providing a mixture of the reaction product from step 4 with from about2% to about 25%, based on the Weight of the oil charged in step 1, ofcalcium hydroxide, and water, at a temperature below the boiling pointof water, (6) substantially completely dehydrating the mixture formed instep 5 and (7) subjecting the dehydrated mixture to filtration to removeinsolubles therefrom.

11. An oil-soluble, phosphorus-, sulfur, and calciumcontaining reactionproduct produced by the method which comprises the steps of (1) forminga mixture comprising (a) a petroleum oil having a molecular weight offrom about 600 to about 1000 and (b) from about 0.5% to about 25% ofcalcium hydroxide, (2) contacting said mixture with an oxidizing gas, ata temperature of from about 125 C. to about 325 C., to effect oxidationof said oil and reaction of said calcium hydroxide with the oxidizedoil, (3) continuing the oxidation for a time sufiicient to incorporatefrom about 0.05% to about 0.5%, by weight, of calcium into the oxidizedoil, (4) reacting the product of step 3 with from about 5% to about 20%,by weight, of phosphorus trisulfide and from about ,05% to about 2% ofsulfur, both percentages being based on the weight of oil charged instep 1, at a temperature of from about 75 C. to about 150 C., to form aphosphorus-, sulfurand calcium-containing product, (5) providing amixture of the reaction product from step 4 with from about 2% to about25 based on the weight of oil charged in step 1, of calcium hydroxide,and water, at

" F; .id hydrocarbon, of a metal hydroxide, the metal constituent ofwhich is selected from Groups I and II of Mendeleeffs Periodic Table ofthe Elements, (2) contacting said mixture with an oxidizing gas at atemperature of from about 125 C. to about 325 C. to effect oxidation of:said hydrocarbon and reaction of said metal hydroxide with the oxidizedhydrocarbon, (3) continuing the oxidation for a time sufiicient toincorporate from about 0.05 to about 3.0%, by weight, of metal into theoxidized hydrocarbon, (4) reacting the product from step 3 with fromabout 5% to about 20%, by weight, based on the weight of hydrocarboncharged in step 1, of a phosphorus sulfide, at a temperature of fromabout C. to about 150 C., to form a phosphorus-, sulfurandmetal-containing product, (5 providing a mixture of the reaction productfrom step 4 with from about 2% to about 25%, by weight, based on thehydrocarbon charged in step 1, of a metal hydroxide, the metalconstituent of which is selected from Groups I and II MendeleetlsFeriodic Table of the Elements, and water, at a temperature below theboiling point of water, (6) substantially completely dehydrating themixture formed in step 5 and (7) subjecting the dehydrated mixture tofiltration to remove insolubles therefrom.

13. A mineral lubricating oil containing a minor amount, sufficient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand metalcontaining oxidized oil reaction product produced by themethod which comprises the steps of (1) forming a mixture comprising (a)a petroleum oil having a molecular weight of from about 200 to about1000 and (b) from about 0.5 to about 25 based on the weight of said oil,of a metal hydroxide, the metal constituent of which is selected fromGroup II of Mendeleeffs Periodic Table of the Elements, (2) contactingsaid mixture with an oxidizing gas at a temperature of from about C. toabout 325 C. to eflfect oxidation of said oil and reaction of said metalhydroxide with the oxidized oil, (3) continuing the oxidation for a timesufiicient to incorporate from about 0.05% to about 3.0%, by weight, ofmetal into the oxidized oil, (4) reacting the product of step 3 withfrom about 5% to about 20%, by weight, based on the oil charged in step1, of a phosphorus sulfide, at a temperature of from about 75 C. toabout C., to form a phosphorus-, sulfurand metal-containing product, (5)providing a mixture of the reaction product from step 4 with from about2% to about 25%, by weight, based on the oil charged in step 1, of ahydroxide of a metal selected from Group II of Mendeleefis PeriodicTable of the Elements, and water, at a temperature below the boilingpoint of water, (6) substantially completely dehydrating the mixtureformed in step 5 and (7) subjecting the dehydrated mixture to filtrationto remove insolubles therefrom.

14. A mineral lubricating oil containing a minor amount, sufiicient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand calcium containing oxidized oil reaction product produced bythe method which comprises the steps of (1) forming a mixture comprising(a) a petroleum oil having a molecular weight of from about 600 to about1000 and (b) from about 0.5 to about 25% of calcium hydroxide, (2)contacting said mixture with an oxidizing gas at a temperature of fromabout 125 C. to about 325 C. to effect-oxidation of said oil andreaction of said calcium hydroxide with the oxidized oil, (3) continuingthe oxidation for a time suflicient to incorporate from about 0.05% toabout 3.0%, by weight, of calcium into the oxidized oil, (4) reactingthe product from step 3 with from about to about 20%, by weight, basedon the hydrocarbon charged in step 1, of a phosphorus sulfide, at atemperature of from about 75 C. to about 150 C., to form a phosphorus-,sulfurand calcium-containing product, (5 providing a mixture of thereaction product from step 4 with from about 2% to about 25%, by weight,based on the Weight of the oil charged in step 1, of calcium hydroxide,and water, at a temperature be low the boiling point of Water, (6)substantially completely dehydrating the mixture formed in step 5 and(7) subjecting the dehydrated mixture to filtration to remove insolublestherefrom.

15. A mineral lubricating oil containing a minor amount, sufiicient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand calcium-containing oxidized oil reaction product produced bythe method which comprises the steps of (1) forming a mixture comprising(a) a petroleum oil having a molecular weight of from about 600 to about1000 and (b) from about 0.5% to about 25%, based on the Weight of saidoil, of calcium hydroxide, (2) contacting said mixture with an oxidizinggas, at a temperature of from about 125 C. to about 325 C., to effectoxidation of said oil and reaction of said calcium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufiicient toincorporate from about 0.05% to about 0.5%, by weight, of calcium intothe oxidized oil, (4) reacting the product from step 3 with from about5% to about 20%, by Weight, based on the weight of oil charged in step1, of phosphorus pentasulfide, at a temperature of from about 75 C. toabout 150 C. to form a phosphorus-, sulfurand calcium-containingproduct, (5) providing a mixture of the reaction product from step 4with from about 2% to about 25%, by Weight, based on the weight of oilcharged in step 1 of calcium hydroxide, and water, at a temperaturebelow the boiling point of water, (6) substantially completelydehydrating the mixture formed in step 5 and (7) subjecting thedehydrated mixture to filtration to remove insolubles therefrom.

16. A mineral lubricating oil containing a minor amount, suflicient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand barium-containing oxidized oil reaction product produced bythe method which comprises the steps (1) forming a mixture comprising(a) a petroleum oil having a molecular weight of from about 600 to about1000 and (b) from about 0.5% to about 25%, based on the Weight of saidoil, of barium hydroxide, (2) contacting said mixture with an oxidizinggas, at a temperature of from about 125 C. to about 325 C., to effectoxidation of said oil and reaction of said barium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufiicient toincorporate from about 0.05% to about 3.0%, by weight, of barium intothe oxidized oi}, (4) reacting the product from step 3 with from about5% to about 20%, by weight, based on the weight of the oil charged instep 1, of a phosphorus sulfide, at a temperature of from about 75 C. toabout 150 C., to form a phosphorus-, sulfurand barium-containingproduct, (5) providing a mixture of the reaction product from step 4with from about 2% to about 25%, by Weight, based on the weight of theoil charged in step 1, of barium hydroxide, and Water, at a temperaturebelow the boiling point of Water, (6) substantially completelydehydrating the" mixture formed in step 5 and (7) subjecting thedehydrated mixture to filtration to remove insolubles therefrom.

17. A mineral lubricating oil containing a minor amount, sufficient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand barium-containing oxidized oil reaction product produced bythe method which comprises the steps of (1) forming a mixture comprising(a) a petroleum oil having a molecular weight of from about 600 to about1000 and (b) from about 0.5 to about 25%, based on the weight of saidoil, of barium hydroxide, (2) contacting said mixture with an oxidizinggas, at a temperature of from about 125 C. to about 325 C., to efiectoxidation of said oil and reaction of said barium hydroxide with theoxidized oil, (3) continuing the oxidation for a time sufficient toincorporate from about 0.05% to 0.5%, by weight, of barium into theoxidized oil, (4) reacting the product from step 3 with from about 5% toabout 20%, by weight, based on the weight of the oil charged in step 1,of phosphorus pentasulfide, at a temperature of from about 75 C. toabout 150 C., to form a phosphorus-, sulfurand barium-containingproduct, (5) providing a mixture of the reaction product from step 4with from about 2% to about 25% by Weight, based on the Weight of oilcharged in step 1, of barium hydroxide, and water, at a temperaturebelow the boiling point of water, (6) substantially completelydehydrating the mixture formed in step 5 and (7) subjecting thedehydrated mixture to filtration to remove insolubles therefrom.

18. A mineral lubricating oil containing a minor amount, sufficient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfur-, calciumand zinc-containing oxidized oil reaction productproduced by the method which comprises the steps of (1) forming amixture comprising (a) a petroleum oil having a molecular weight of fromabout 600 to about 1000 and (b) from about 0.5% to about 25%, based onthe weight of said oil, of calcium hydroxide, (2) contacting saidmixture with an oxidizing gas at a temperature of from about 125 C. toabout 325 C. to efi'ect oxidation of said oil and reaction of saidcalcium hydroxide with the oxidized oil, (3) continuing the oxidationfor a time sufficient to incorporate from about 0.05% to about 3.0%, byweight, of calcium into the oxidized oil, ('4) reacting the product fromstep 3 with from about 5% to about 20%, by weight, based on the weightof oil charged in step 1, of a phosphorus sulfide at a temperature offrom about C. to about 150 C. to form a phosphorus-, sulfurandcalcium-containing product, (5) providing a mixture of the reactionproduct from step 4 with zinc hydroxide and water at a temperature belowthe boiling point of water, (6) substantially completely dehydrating themixture formed in step 5 and (7) subjecting the dehydrated mixture tofiltration to remove insolubles therefrom.

19. A mineral lubricating oil containing a minor amount, suificient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfun, calciumand zinc-containing oxidized oil reaction productproduced by the method which comprises the steps of (1) forming amixture comprising (a) a petroleum oil having a molecular weight of fromabout 600 to about 1000 and (b) from about 0.5% to about 25 based on theweight of said oil, of calcium hydroxide, (2) contacting said mixturewith an oxidizing gas, at a temperature of from about C. to about 325C., to effect oxidation of said oil and reaction of said calciumhydroxide with the oxidized oil, (3) continuing the oxidation for a timesuflicient to incorporate from about 0.05% to 0.5 by weight, of metalinto the oxidized oil, (4) reacting the product from step 3 with fromabout 5% to about 20%, by weight, based on the weight of oil charged instep 1, of phosphorus pentasulfide, at a temperature of from about 75 C.to about C., to form a phosphorus-, sulfurand calcium-containingproduct, (5 providing a mixture of the reaction product from step 4 withfrom about 2% to about 25%, based on the Weight of the oil charged instep 1, of zinc hydroxide, and water, at a temperature below the boilingpoint of Water, (6) substantially completely dehydrating the mixtureformed in step 5 and (7) subjecting the dehydrated mixture to filtrationto remove insolubles therefrom.

20. A mineral lubricating oil containing a minor amount, sufiicient toimprove the detergent'character thereof, of an oil-soluble, phosphorus-,sulfurand calcium-containing oxidized oil reaction product produced bythe method which comprises the steps of (1) forming a mixture comprising(a) a petroleum oil having a molecular weight of from about 600 to about1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2)contacting said mixture with an oxidizing gas, at a temperature of fromabout 125 C. to about 325 C., to effect oxidation of said oil andreaction of said calcium hydroxide with the oxidized oil, (3) continuingthe oxidation for a time sufiicient to incorporate from about 0.05% toabout 0.5%, by weight, of calcium into the oxidized oil, (4) reactingthe product from step 3 with from about 5% to about by weight, based onthe weight of oil charged in step 1, of phosphorus heptas'ulfide, at atemperature of from about 75 C. to about 150 C., to form a phosphorus-,sulfurand calcium-containing product, (5) providing a mixtureof thereaction product from step 4 with from about 2% to about by weight,based on the weight of oil charged in step 1, of calcium hydroxide, andwater, at a temperature below the boiling point of water, (6)substantially completely dehydrating the mixture formed in step 5 and(7) subjecting the dehydrated mixture to filtration to remove insolublestherefrom.

21. A mineral lubricating oil containing a minor amount, sufiicient toimprove the detergent character thereof, of an oil-soluble,phosphorus-,sulfurand calciumcontaining oxidized oil reaction productproduced by the method which comprises the steps of (1) forming amixture comprising (a) a petroleum oil having a molecular weight of fromabout 600 to about 1000 and (b) from about 0.5% to about 25% of calciumhydroxide, (2) contacting said mixture with an oxidizing gas, at atempera ture of from about 125 C. to about 325 C., to effect oxidationof said oil and reaction of said calcium hydroxide With the oxidizedoil, (3) continuing the oxidation for a time sufficient to incorporatefrom about 0.05% to about 0.5%, by weight, of calcium into the oxidizedoil, (4) reacting the product of step 3 with from about 5% to about 20%,by weight, based on the weight of the oil charged in step 1, ofphosphorus trisulfide, at a temperature of from about C. to about C., toform a phosphorus-, sulfurand calcium-containing product, (5) providinga mixture of the reaction product from step 4 with from about 2% to'about 25 based onthe weight of the oil charged in step 1, of calciumhydroxide and water, at a temperature below the boiling point of water,(6) substantially completely dehydrating the mixture formed in step 5and (7) subjecting the dehydrated mixture to filtration to removeinsolubles therefrom.

22. A mineral lubricating oil containing a minor amount, sufficient toimprove the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand calcium-containing reaction product produced by the methodwhich comprises the steps of (1) forming a mixture comprising (a) apetroleum oil having a molecular weight of from about 600 to about 1000and (b) from about 0.5% to about 25 of calcium hydroxide, (2) contactingsaid mixture with an oxidizing gas, at a temperature of from about 125C. to about 325 C., to effect oxidation of said oil and reaction of saidcalcium hydroxide with the oxidized oil, (3) continuing the oxidationfor a. time sulficient to incorporate from about 0.05% to about 0.5%, byweight, of calcium into the oxidized oil, (4) reacting the product ofstep 3 with from about 5% to about 20%, by weight, of phosphorustrisulfide and from about .05 to about 2% of sulfur, both percentagesbeing based on the weight of oil charged in step 1, at a temperature offrom about 75 C. to about C., to form a phosphorus-, sulfurandcalcium-containing product, (5 providing a mixture of the reactionproduct from step 4 with from about 2% to about 25 based on the weightof oil charged in step 1, of calcium hydroxide, and water, at atemperature below the boiling point of water, (6) substantiallycompletely dehydrating the mixture formed in step 5 and (7) subjectingthe dehydrated mixture to filtration to remove insolubles therefrom.

References Cited in the file of this patent UNITED STATES PATENTSMusselman Apr. 22, 1947

1. AN OIL-SOLUBLE, PHOSPHORUS-, SULFUR- AND METAL-CONTAINING OXIDIZEDHYDROCARBON REACTION PRODUCT PRODUCED BY THE METHOD WHICH COMPRISES THESTEP OF (1) FORMING A MIXING COMPRISING (A) A HYDROCARBON HAVING AMOLECULAR WEIGHTS OF FROM ABOUT 200 TO 1000 AND WHICH IS SELECTED FROMTHE GROUP CONSISTING OF ALIPHATIC HYDROCARBONS AND AROMATIC HYDROCARBONHAVING AT LEAST ONE NUCLEAR HYDROGEN ATOM SUBSTITUTED BY AN ALIPHATICRADICAL TO PROVIDE A TOTAL OF AT LEAST 8 ALIPHATIC RADICAL PER MOLETHEREIN, AND MIXTURES THEREOF, AND (B) FROM ABOUT 0.5% TO ABOUT 25%,BASED ON THE WEIGHT OF SAID HYDROCARBON OF A METAL HYDROXIDE, THE METALCONSTITUENT OF WHICH IS SELECTED FROM GROUPS I AND II OF MENDELEEFF''SPERIODIC TABLE OF THE ELEMENTS (2) CONTACTING SAID MIXTURE WITH ANOXIDIZING GAS AT A TEMPERATURE OF FROM ABOPUT 125* C. TO ABOUT 325* C.TO EFFECT OXIDATION OF SAID HYDROCARBON AND REACTION OF SAID METALHYDROXIDE WITH THE OXIDIZED HYDROCARBON, (3) CONTINUING THE OXIDATIONFOR A TIME SUFFICIENT TO INCORPORATE FROM ABOUT 0.05% TO ABOUT 3.0% BYWEIGHT, OF METAL, INTO THE OXIDIZED HYDROCARBON (4) REACTING THE PRODUCTFROM STEP 3 WITH FROM ABOUT 5% TO ABOUT 20%, BY WEIGHT, BASED ON THEWEIGHT OF HYDROCARBON CHARGED IN STEP 1, OF A PHOSPHORUS SULFIDE, AT ATEMPERATURE OF FROM ABOUT 75* C. TO ABOUT 150* C., TO FORM APHOSPHORUS-, SULFUR, AND METAL-CONTAINING PRODUCT, (5) PROVIDING AMIXTURE OF THE REACTION PRODUCT FROM STEP 4 WITH FROM ABOUT 2% TO ABOUT25% BY WEIGHT BASED ON THE HYDROCARBON CHARGED IN STEP 1, OF A METALHYDROXIDE, THE METAL CONSTITUENT OF WHICH IS SELECTED FROM GROUPS I ANDII OF MENDELEEF''S PERIODIC TABLE OF THE ELEMENTS, AND WATER, AT ATEMPERATURE BELOW THE BOILING POINT OF WATER, (6) SUBSTANTIALLYCOMPLETELY DEHYDRATING THE MIXTURE FORMED IN STEP 5 AND (7) SUBJECTINGTHE DEHYDRATED MIXTURE OF FILTRATION TO REMOVE INSOLUBLES THEREFROM.